CN100355818C - Composite formed article comprising vulcanized rubber and thermoplastic elastomer and use thereof - Google Patents

Composite formed article comprising vulcanized rubber and thermoplastic elastomer and use thereof Download PDF

Info

Publication number
CN100355818C
CN100355818C CNB2004800102921A CN200480010292A CN100355818C CN 100355818 C CN100355818 C CN 100355818C CN B2004800102921 A CNB2004800102921 A CN B2004800102921A CN 200480010292 A CN200480010292 A CN 200480010292A CN 100355818 C CN100355818 C CN 100355818C
Authority
CN
China
Prior art keywords
vulcanized rubber
rubber
thermoplastic elastomer
weight
formed body
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CNB2004800102921A
Other languages
Chinese (zh)
Other versions
CN1774466A (en
Inventor
今井正
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsui Chemicals Inc
Mitsui Chemical Industry Co Ltd
Original Assignee
Mitsui Chemical Industry Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsui Chemical Industry Co Ltd filed Critical Mitsui Chemical Industry Co Ltd
Publication of CN1774466A publication Critical patent/CN1774466A/en
Application granted granted Critical
Publication of CN100355818C publication Critical patent/CN100355818C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
    • C08J5/121—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives by heating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/68—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts by incorporating or moulding on preformed parts, e.g. inserts or layers, e.g. foam blocks
    • B29C70/84—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts by incorporating or moulding on preformed parts, e.g. inserts or layers, e.g. foam blocks by moulding material on preformed parts to be joined
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/68—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts by incorporating or moulding on preformed parts, e.g. inserts or layers, e.g. foam blocks
    • B29C70/84—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts by incorporating or moulding on preformed parts, e.g. inserts or layers, e.g. foam blocks by moulding material on preformed parts to be joined
    • B29C70/845—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts by incorporating or moulding on preformed parts, e.g. inserts or layers, e.g. foam blocks by moulding material on preformed parts to be joined by moulding material on a relative small portion of the preformed parts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60J—WINDOWS, WINDSCREENS, NON-FIXED ROOFS, DOORS, OR SIMILAR DEVICES FOR VEHICLES; REMOVABLE EXTERNAL PROTECTIVE COVERINGS SPECIALLY ADAPTED FOR VEHICLES
    • B60J10/00—Sealing arrangements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60J—WINDOWS, WINDSCREENS, NON-FIXED ROOFS, DOORS, OR SIMILAR DEVICES FOR VEHICLES; REMOVABLE EXTERNAL PROTECTIVE COVERINGS SPECIALLY ADAPTED FOR VEHICLES
    • B60J10/00—Sealing arrangements
    • B60J10/15—Sealing arrangements characterised by the material
    • B60J10/16—Sealing arrangements characterised by the material consisting of two or more plastic materials having different physical or chemical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60J—WINDOWS, WINDSCREENS, NON-FIXED ROOFS, DOORS, OR SIMILAR DEVICES FOR VEHICLES; REMOVABLE EXTERNAL PROTECTIVE COVERINGS SPECIALLY ADAPTED FOR VEHICLES
    • B60J10/00—Sealing arrangements
    • B60J10/20—Sealing arrangements characterised by the shape
    • B60J10/21—Sealing arrangements characterised by the shape having corner parts or bends
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60J—WINDOWS, WINDSCREENS, NON-FIXED ROOFS, DOORS, OR SIMILAR DEVICES FOR VEHICLES; REMOVABLE EXTERNAL PROTECTIVE COVERINGS SPECIALLY ADAPTED FOR VEHICLES
    • B60J10/00—Sealing arrangements
    • B60J10/20—Sealing arrangements characterised by the shape
    • B60J10/23—Sealing arrangements characterised by the shape assembled from two or more parts
    • B60J10/233—Modular sealing arrangements, i.e. arrangements built up from a large number of joined modules
    • B60J10/2335—Modular sealing arrangements, i.e. arrangements built up from a large number of joined modules with joint end members, e.g. abutting ends
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B29C45/14336—Coating a portion of the article, e.g. the edge of the article
    • B29C45/14409—Coating profiles or strips by injecting end or corner or intermediate parts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
    • B60R13/00—Elements for body-finishing, identifying, or decorating; Arrangements or adaptations for advertising purposes
    • B60R13/06—Sealing strips
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31909—Next to second addition polymer from unsaturated monomers
    • Y10T428/31913—Monoolefin polymer

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Seal Device For Vehicle (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)

Abstract

A formed vulcanized rubber article (1) which comprises 2 to 10 wt % of an olefinic resin exhibiting a crystallinity of 10 % or more as measured with a differential scanning calorimeter (DSC); and a composite formed article which comprises said formed vulcanized rubber article (1) and, joined thereto, a formed article (2) comprising a thermoplastic elastomer containing more than 10 % of an olefinic resin exhibiting a crystallinity of 10 % or more as measured with a differential scanning calorimeter (DSC) and having a gel content of 30 wt % or less. The formed vulcanized rubber article can form, through melt adhesion and without the use of an adhesive layer, a composite formed article which exhibits satisfactory adhesion strength and causes the parent material failure upon pealing. The above composite formed article is advantageously used for an interior or exterior material for an automobile, in particular, for a weatherstrip material.

Description

Composite shaped body that vulcanized rubber and thermoplastic elastomer constitute and uses thereof
Technical field
The present invention relates to composite shaped body (being also referred to as molded composite material) with and uses thereof, this composite shaped body is that welding moulding thermoplastic elastomer and vulcanized rubber form, specifically, particularly as automobile weather strip (weather strip), door sealing turnings such as (door trim) abnormity interconnecting piece or special-shaped end fitting.
Background technology
In the past, have connecting portion weather strip manufacturing processed normally, to cut out by the sulfidization molding product of extruding that ethylene-propylene-non-conjugated diene terpolymers (EPDM) rubber stock constitutes, one side or two sides' metal pattern is installed, in the die cavity that forms, inject rubber stock and the congener rubber-moulding material of this EPDM, carry out sulfidization molding.
On the other hand, as this formed material, from the viewpoint of productivity, environmental compatibility and lightness,, bring into use the thermoplastic elastomer (composition) that does not need vulcanization process as substituting of the vulcanized rubber that uses ethylene-propylene-non-conjugated diene terpolymers (EPDM).
But usually, it is bonding etc. that vulcanized rubber and thermoplastic elastomer can not vulcanize, though the past is integrated with it with caking agent, from productivity or to the consideration of environment, it is inadequate.
As the technology that improves cementability by the composition that changes thermoplastic elastomer, can enumerate the method (for example, Japanese patent laid-open 2-115249 communique, spy open flat 8-244068 communique, the spy opens flat 10-324200 communique) of in thermoplastic elastomer, adding the resin that contains polar group.
In addition, also has the method (for example, Japanese patent laid-open 9-40814 communique) of before thermoplastic elastic is body formed, adding specific ethene-1-octene copolymer.
As the technology that improves cementability by the composition that changes vulcanized rubber, can enumerate the polyacrylic method (for example with reference to Japanese patent laid-open 10-7849 communique) of in existing vulcanized rubber, adding micro-crystalline.But if add the polypropylene of the micro-crystalline as the atactic polypropylene(APP), the elasticity that existing vulcanized rubber takes place sometimes reduces, perhaps through the time after being clamminess etc. of moulding product.
Except the technology of the composition of above relevant thermoplastic elastomer or vulcanized rubber, also have, after cutting out vulcanized rubber, it is concavo-convex to give cut surface, makes its technology that obtains cementation effect (anchoreffect) (for example with reference to Japanese patent laid-open 9-118133 communique); In the technology (for example opening flat 6-47816 communique) of the cut surface of vulcanized rubber coating polyolefin resin powder etc. with reference to the spy.
Summary of the invention
The present invention relates to vulcanized rubber formed body and uses thereof, more particularly, be particularly related to vulcanized rubber formed body that the welding moulding is suitable for during as the thermoplastic elastomer of turnings such as automobile weather strip, door sealing abnormity interconnecting piece or special-shaped end fitting and uses thereof.
The present invention seeks to, be provided at and do not use bond layer and during the welding heat thermoplastic elastic, can form the vulcanized rubber formed body have sufficient adhesion strength and to produce the formed body of wood destruction when peeling off, and on this vulcanized rubber formed body the molded composite material of welding heat thermoplastic elastic.
Vulcanized rubber formed body of the present invention is, be used for vulcanized rubber formed body with the olefin hydrocarbons thermoplasticity elastic body welding, and it is characterized in that the crystallization degree that contains useful differential scanning type calorimeter (DSC) mensuration is olefine kind resin 2～10 weight % more than 10%.In addition, molded composite material of the present invention, it is characterized in that: by containing vulcanized rubber formed body (1) that crystallization degree that useful differential scanning type calorimeter (DSC) measures is olefine kind resin 2～10 weight % 10% or more and being that to surpass 10 weight % and gel fraction be that formed body (2) joint of the thermoplastic elastomer formation below the 30wt% forms for the content of the olefine kind resin 10% or more by the crystallization degree of measuring with differential scanning type calorimeter (DSC).Above-mentioned molded composite material is preferred for the automobile inside/outside decorative material, is particularly preferred for the weather strip purposes.
Description of drawings
Fig. 1 (A) schematically represents automobile that line part forms by composition for thermoplastic elastomer by vulcanized rubber formed body, the corner part stereographic map with an example of weather strip.Fig. 1 (B) is the stereographic map for the formation method of the corner part that this weather strip schematically is described.
Embodiment
Below the vulcanized rubber formed body of being correlated with regard to the present invention and uses thereof be elaborated.
The vulcanized rubber formed body
The vulcanized rubber formed body that the present invention relates to contains the olefine kind resin of 2～10 weight %.
The definition of " sulfuration " of the present invention is, for example in the polymer dictionary (ball is apt to Co., Ltd., 1994 annuals) defined have a corsslinking molecular network structure, vulcanized rubber is a crosslinked rubber fully.
With vulcanized rubber blended olefine kind resin be, the crystallization degree of measuring with differential scanning type calorimeter (DSC) is the olefine kind resin 10% or more, can enumerate carbonatoms 2～20, the preferably homopolymer or the interpolymer of the alpha-olefin of carbonatoms 2～10 as this olefine kind resin.
Alpha-olefin as carbonatoms 2～10, specifically can enumerate ethene, propylene, 1-butylene, the 1-amylene, 4-methyl-1-pentene, the 1-hexene, the 1-heptene, the 1-octene, the 1-nonene, 1-decene, the 1-undecylene, the 1-dodecylene, the 1-tridecylene, tetradecene, 1-15 carbenes, cetene, the 1-heptadecene, the 1-vaccenic acid, 1-19 carbenes, the 1-eicosylene, 3-methyl-1-butene, the 3-Methyl-1-pentene, 3-ethyl-1-amylene, 4-methyl-1-pentene, 4-methyl isophthalic acid-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-amylene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 9-methyl isophthalic acid-decene, 11-methyl isophthalic acid-dodecylene, 12-ethyl-tetradecene, and their composition.
Melt flow (the MFR of such olefine kind resin; ASTMD1238,190 ℃, load 2.16kg) be preferably 0.01～500g/10 branch, more preferably 0.1～100g/10 branch.In addition, " η " of such olefine kind resin (at naphthalane, the limiting viscosity of measuring in 135 ℃) is 0.1～10dl/g, is preferably 0.5～5dl/g.
As the concrete example of implementing olefine kind resin, can enumerate polyethylene, polypropylene, polybutene etc., preferred especially new LDPE (film grade), straight-chain low density polyethylene, polypropylene.
The density of new LDPE (film grade) of the present invention, straight-chain low density polyethylene (ASTMD1505) expected value is 0.870～0.94g/cm 3, be preferably 0.875～0.935g/cm 3, 0.880～0.930g/cm more preferably 3
In addition, new LDPE (film grade) of the present invention, straight-chain low density polyethylene in its DSC measures, 80～140 ℃, preferably 90～130 ℃, more preferably have at least 1 endotherm(ic)peak (Tm) at 100～130 ℃.In addition, DSC measures, sample is filled in the aluminium dish, according to be warmed up to 200 ℃ with 100 ℃/minute speed, after 200 ℃ keep 10 fens, with 100 ℃/minute speed, cool to till-150 ℃, then the endothermic curve when heating up with 10 ℃/minute speed is tried to achieve.
This new LDPE (film grade), straight-chain low density polyethylene be, crystallinity ethylene-alpha-ethenyl copolymer that ethylene homo body or ethene and carbonatoms 3～20, preferred 3～8 alpha-olefin constitute.When containing comonomer, the content of its comonomer is a small amount of, and 25 moles that are integral body below the %.
The new LDPE (film grade) that uses among the present invention, straight-chain low density polyethylene normally, the crystallization degree of measuring with differential scanning type calorimeter (DSC) is the material more than 10%.In addition, can enumerate ethene-1-butylene interpolymer, ethylene-propylene copolymer body, ethene-hervene copolymer body, ethylene-octene interpolymer etc., be preferably selected from more than at least a kind of new LDPE (film grade) and straight-chain low density polyethylene.For example, can be the mixture more than 2 kinds, also can be by high density polyethylene(HDPE) and 2 kinds of materials that constitute of new LDPE (film grade).In addition, can also be the material that constitutes by new LDPE (film grade) more than 2 kinds, the material that constitutes by straight-chain low density polyethylene more than 2 kinds.In addition, the catalyzer of using during to manufacturing crystallinity ethylene-like polymer zoarium etc. is not particularly limited, and can make by common strange lattice Alan Jay Lerner tower (ziegler-natta) catalyzer or metallocene catalyst.
Melt flow (the MFR of the new LDPE (film grade) of using among the present invention, straight-chain low density polyethylene; ASTMD1238,190 ℃, load 2.16kg) expectation is preferably below 0.01～500g/10 divides, and is generally 0.1～100g/10 branch, below more preferably 0.5～50g/10 divides.
As the polypropylene of using among the present invention, can enumerate the propylene homopolymer and with the alpha-olefin random copolymerization of propylene and ethene and/or carbonatoms 4～20 or the copolymerization of propylene body of block copolymerization.
As the alpha-olefin of carbonatoms 4～20, specifically can enumerate above-mentioned alpha-olefin.As with the comonomer of copolymerization of propylene, optimal ethylene, 1-butylene.
From the formation monomer content (propylene content) of propylene derived, be generally 50～90 weight % in this copolymerization of propylene body, the formation monomer content (co-monomer content) from comonomer-derived is generally 50～10 weight %.In addition, the composition of copolymerization of propylene body can be measured by 13C-NMR and obtain.
Polyacrylic melt flow (MFR; ASTMD1238,230 ℃, load 2.16kg) expectation is generally 0.01～100g/10 branch, is preferably 0.1～80g/10 branch, 0.3～60g/10 branch more preferably.
The polyacrylic fusing point of being measured by DSC (Tm) is generally below 170 ℃.
The content of the olefine kind resin of above-mentioned vulcanized rubber formed body is that 2 weight % are above, 10 weight % following, be preferably 3 weight %～8 weight %, 4 weight %～5 weight % more preferably.(gross weight in the vulcanized rubber formed body is 100 weight %.)
As the vulcanized rubber formed body that the present invention relates to, preferably its main component is an ethylene-alpha-olefin-nonconjugated polyene hydrocarbon interpolymer rubber.As the alpha-olefin in the ethylene-alpha-olefin-nonconjugated polyene hydrocarbon interpolymer rubber, the alpha-olefin of preferred carbonatoms 3～20 specifically can be enumerated above-mentioned alpha-olefin.The alpha-olefin of preferred especially carbonatoms 3～8, for example propylene, 1-butylene, 4-methyl-1-pentene, 1-hexene, 1-octene in these alpha-olefins.
Viewpoint from the rubber combination of the vulcanized rubber formed body that can access the ageing resistance that can provide outstanding, outstanding strength characteristics, outstanding caoutchouc elasticity, outstanding winter hardiness and outstanding processibility, ethylene-alpha-olefin-nonconjugated polyene hydrocarbon interpolymer rubber is preferably with 50/50～90/10[(a)/(b)] mol ratio contain (a) from the monomer of ethylene derivative with (b) from the alpha-olefin derived monomer of carbonatoms 3～20.More preferably this mol ratio is 65/35～90/10, more preferably 65/35～85/15, is preferably 65/35～80/20 especially.
In addition, as the unconjugated polyene hydrocarbon, specifically be preferably: 1,4-hexadiene, 3-methyl isophthalic acid, 4-hexadiene, 4-methyl isophthalic acid, 4-hexadiene, 5-methyl isophthalic acid, 4-hexadiene, 4,5-dimethyl-1,4-hexadiene, 7-methyl isophthalic acid, 6-octadiene, 8-methyl-4-ethylidene-1,7-nonadiene, 4-ethylidene-1, chain non-conjugated dienes such as 7-11 carbon diene;
Ring-type non-conjugated dienes such as methyltetrahydro indenes (methyl tetrahydroindene), 5-ethylidene-2-norbornene (5-Ethylidene-2-norbornene), 5-methylene-2-norbornene, 5-isopropylidene-2-norbornylene, 5-vinylidene-2-norbornylene, 6-chloromethyl-5-isopropenyl-2-nirbornene, 5-vinyl-2-norbornylene, 5-isopropenyl-2-nirbornene, 5-isobutenyl-2-norbornylene, cyclopentadiene, norbornadiene;
2,3-isopropylidene-5-norbornylene, 2-ethylidene-3-isopropylidene-5-norbornylene, 2-propenyl-2,2-norbornadiene, 4-ethylidene-8-methyl isophthalic acid, triolefins such as 7-nonadiene etc.Wherein, preferred 5-ethylidene-2-norbornene, 5-vinyl-2-norbornylene, cyclopentadiene, 4-ethylidene-8-methyl isophthalic acid, 7-nonadiene.
These unconjugated polyene hydrocarbon can separately or make up more than 2 kinds and use.
The iodine number of ethylene-alpha-olefin-nonconjugated polyene hydrocarbon interpolymer rubber, can obtain the high rubber combination of cross-linking efficiency, the rubber combination of the vulcanized rubber formed body of the compression deformability that can obtain to provide outstanding, and, from helping the viewpoint of cost, be preferably 1～40, more preferably 1～30.
Viewpoint from the rubber combination of the vulcanized rubber formed body of strength characteristics, compression deformability and the processibility that can obtain to provide outstanding, the mooney viscosity (Mooney viscosity) of ethylene-alpha-olefin-nonconjugated polyene hydrocarbon interpolymer rubber [ML1+4 (125 ℃)] is preferably 10～250, more preferably 40～150.These ethylene-alpha-olefin-nonconjugated polyene hydrocarbon interpolymer rubber can use separately, also can make up more than 2 kinds and use.
In the vulcanized rubber,,, preferably use the carbon black of 30～300 weight part ratios with respect to 100 parts by weight of ethylene-alpha-olefin-nonconjugated polyene hydrocarbon interpolymer rubber in order to obtain having the extruding, forming and vulcanization rubber of sufficient mechanical.
Can use carbon blacks such as SRF, GPF, FEF, MAF, HAF, ISAF, SAF, FT, MT as carbon black.From the viewpoint of the rubber combination of the good vulcanized rubber formed body of the physical strength that can obtain providing outstanding and product surface, the nitrogen adsorption specific surface area of preferred carbon black is 10～100m 2/ g.
In the vulcanized rubber,, can mix mixtures such as existing known protective agent, processing aid, whipping agent, frothing aid, tinting material, dispersion agent, fire retardant according to the purposes of purpose sulfide.
In addition, in vulcanized rubber, can suitably use inorganic filler according to purposes, usually,, use 100 weight parts at the most with respect to 100 parts by weight of ethylene-alpha-olefin-nonconjugated polyene hydrocarbon interpolymer rubber as toughener.
As inorganic filler, specifically can enumerate silicon-dioxide, soft lime carbonate, water-ground limestone, talcum, clay etc.
As blended tenderizer in the vulcanized rubber, can use the tenderizer that is generally used for rubber.Specifically can enumerate petroleum-type tenderizers such as process oil (process oil), lubricating oil, paraffin, liquid paraffin, polyethylene wax, Poly Propylene Wax, petroleum pitch, Vaseline;
Coal tar such as coal tar, coal-tar pitch oil-softener;
Viscotrol C, linseed oil, rapeseed oil, soybean oil, coconut wet goods fatty oils tenderizer;
Yatall MA;
Sub, (factice (factis));
Wax classes such as beeswax, carnauba wax, lanolin;
Lipid acid and soaps such as ricinolic acid, palmitinic acid, stearic acid, barium stearate, calcium stearate, zinc laurate;
Naphthenic acid;
Pine tar, rosin or derivatives thereof;
Synthetic polymers such as terpine resin, petroleum resin, chroman-indene resin (chroman indeneresin), atactic polypropylene(APP);
Ester class tenderizers such as dioctyl phthalate (DOP), Octyl adipate, dioctyl sebacate;
Microcrystalline Wax, liquid polybutadiene, modified liquid polyhutadiene, liquid polyisoprene, terminal-modified polyisoprene, the terminal-modified isoprene of hydrogenation, liquid polysulfide rubber, the lubricated wet goods of hydrocarbon synthesis.Wherein, preferably use the petroleum-type tenderizer, especially preferably use process oil.Suitably select the combined amount of these tenderizers according to the purposes of sulfide.
As the sulfurized vulcanizing agent that is used for vulcanized rubber, can enumerate sulphur and sulphur compound.In addition, so-called here vulcanized rubber is not only with sulfur-crosslinked material, also comprises with the crosslinked material of other linking agents.
Specifically can enumerate powder sulphur, precipitated sulfur, sulfoid, surface treatment sulphur, insoluble sulfur etc. as sulphur.
Specifically can enumerate sulfur subchloride, sulfur dichloride, polymer polysulfide etc. as sulphur compound.In addition, can also use and under curing temperature, emit sulphur and carry out sulfurized sulfide, for example dithiomorpholine, alkyl phenol disulfide, tetramethyl-thiuram disulfide, dipentamethylene thiuram tetrasulfide, dimethyl dithiocarbamate selenium etc.
Wherein, preferred sulphur.
Usually with respect to the above-mentioned interpolymer rubber of 100 weight parts, use the sulphur or the sulfide of 0.1～10 weight part ratio.
In addition, when using sulphur or sulfide, preferred and use vulcanization accelerator as vulcanizing agent.As vulcanization accelerator, specifically can enumerate N-cyclohexyl-2-[4-morpholinodithio sulfinyl amine (CBS), N-oxydiethylene--2-[4-morpholinodithio sulfinyl amine (OBS), the N-tertiary butyl-2-[4-morpholinodithio sulfinyl amine (BBS), N, N-di-isopropyl-sulfinyl amine compounds such as 2-[4-morpholinodithio sulfinyl amine;
Benzothiazole compounds such as 2-mercaptobenzothiazole (MBT), 2-(2, the 4-dinitrophenyl) mercaptobenzothiazole, 2-(4-morpholino sulfo-) benzothiazole, 2-(2,6-diethyl-4-morpholino sulfo-) benzothiazole, dibenzothiazyl disulfide;
Guanidine compounds such as vulkacit D (DPG), triphenyl guanidine, di-o-tolylguanidine (DOTG), orthotollyl biguanide, diphenyl guanidine naphthalate;
Aldehyde amine or aldehyde-ammoniac compounds such as acetaldehyde aniline condensate, butyl aldehyde aniline condensation product, vulkacit H (H), aldamine;
Imidazolines such as 2-mercaptoimidazoline;
Thioureas such as thiocarbanilide, diethyl thiourea (EUR), dibutyl thiourea, trimethyl thiourea, diorthotollyl thiourea;
Sulfuration tetra methylthiuram (TMTM), tetramethyl-thiuram disulfide (TMTD), tetraethylthiuram disulfide, tetrabutylthiuram disulfide, curing four (2-ethylhexyl) thiuram (TOT), dipentamethylene thiuram tetrasulfide thiuram compounds such as (TRA);
Dithiocar-bamate such as dimethyl dithiocarbamate zinc, diethyldithio-carbamate zinc, zinc dibutyl dithiocaarbamate, zinc-ethylphenyl dithiocarbamate, butyl phenyl zinc dithiocarbamate, Sodium dimethyldithiocarbamate 40min, Selenium dimethyl dithiocarbamate, tellurium dimethyldithiocarbamate;
Xanthogenate such as dibutyl xanthogenic acid zinc;
Zinc white compounds such as (zinc oxide).
These vulcanization accelerators with respect to the above-mentioned interpolymer rubber of 100 weight parts, use 0.1～20 weight part ratio usually.
As the antiaging agent that uses in the vulcanized rubber, can enumerate for example amine, Hinered phenols or sulphur class antiaging agent etc., these antiaging agents use in the scope of not destroying the object of the invention.
Can enumerate diphenylamine, phenylenediamine etc. as the amine antiaging agent.
As sulphur class antiaging agent, be used for the sulphur class antiaging agent of rubber usually.
Can use the processing aid that is generally used for Rubber processing as processing aid.Specifically, can enumerate senior lipid acid such as linolic acid, ricinolic acid, stearic acid, palmitinic acid, lauric acid; Senior soaps such as barium stearate, Zinic stearas, calcium stearate; The ester class of above-mentioned higher fatty acid etc.
Such processing aid with respect to 100 parts by weight of ethylene-alpha-olefin-nonconjugated polyene hydrocarbon copolymer rubber, uses the following amount of 10 weight parts usually, and preferred physics value as requested decides only amount.
As whipping agent, specifically can enumerate inorganic foaming agents such as sodium bicarbonate, yellow soda ash, bicarbonate of ammonia, volatile salt, ammonium nitrite; N, N '-dimethyl-N, N '-dinitrosoterephthalamine, N, N '-dinitrosopentamethylene tetramine nitroso compounds such as (DPT); Azo-compounds such as azoformamide (ADCA), Diisopropyl azodicarboxylate (AZBN), azo dicyclohexyl nitrile, nitrogen benzide diamines, barium azodicarboxylate; Benzol sulfohydrazide (BSH), toluene sulfonyl hydrazide (TSH), P, P '-bis oxide (benzene sulfonyl) hydrazine (p, p '-oxybis (benzene sulfonyl hydrazide)) (OBSH), sulfobenzide-3, benzol sulfohydrazide compounds such as 3 '-two benzol sulfohydrazides; Nitrogen calcium, 4 repeatedly, 4-phenylbenzene disulfonyl nitrogen (4,4-diphenyl disulfonyl azide), the p-tolylsulfonyl triazo-compounds such as nitrogen that change that change.
In addition, can mix known other rubber in the composition of vulcanized rubber uses.As other such rubber, can enumerate natural rubber (NR), synthetic polyisoprene isoamyl class rubber such as (IR), divinyl rubber (BR), styrene butadiene rubbers (SBR), acrylonitrile-butadiene rubber (NBR), neoprene (CR) equiconjugate polydiene.
[configuration of rubber combination and vulcanized rubber formed body thereof]
Used rubber combination during the modulation of vulcanized rubber formed body, can modulate by the following method: by picture Banbury (Banbury mixer), kneading machine, internal mixer (internal mixer) class that mixing roll is such, with ethylene-alpha-olefin-nonconjugated polyene hydrocarbon interpolymer rubber, carbon black, rubber stiffener, inorganic filler, additives such as tenderizer, under 80～170 ℃ temperature after mixing 2～20 minutes, with vulcanizing agents such as sulphur with cylinder or kneading machines such as opening cylinders, append vulcanization accelerator according to necessity, vulcanization aid, whipping agent, frothing aid mixes, after 40～80 ℃ of bowl temperatures are descended mixing 5～30 minutes, tell.
Synthetic like this extrusion moulding rubber combination becomes the purpose shape by extrusion shaping machine, in the time of moulding, by forming composition is imported in the truck for vulcanlzing pan, heats under 140～300 ℃ temperature 1～20 fen, can vulcanize.
Vulcanization process carries out usually continuously.As the heating means in the truck for vulcanlzing pan, can use heater meanses such as warm air, granulated glass sphere thermopnore, molten salt bath (LCM), PCM (Powder Curing Medium or Powder Curing Method), UHF (uhf electromagnetic wave), steam.
Vulcanized rubber formed body of the present invention can not be measured even formed body is pulverized mensuration mobile (for example MFR) by gelation.
Olefin hydrocarbons thermoplasticity elastic body
Olefin hydrocarbons thermoplasticity elastic body among the present invention, " olefin hydrocarbons thermoplasticity elastic body " be meant, the thermoplastic elastomer that is made of olefine kind resin and rubber.
For example in the polymer voluminous dictionary (ball is apt to Co., Ltd., 1994 annuals), following explanation is arranged: thermoplastic elastomer has and physical properties like the rubber-like, and for example flexibility and bounce-back property are processed with the common opposite thermoplastic elastomer that can be used as of rubber.
And the content of the olefine kind resin of the thermoplastic elastomer that the present invention is correlated with has surpassed 10 weight %, preferred 15～70 weight %, more preferably 20～60 weight %.
Employed thermoplastic elastomer is among the present invention, forms the thermoplastic elastomer of the form of island structure, and the median size of island phase is below the 2 μ m.And the island mainly is made of crosslinked (gelation) composition mutually.So-called here island structure is meant and has the phase structure of disperseing example in the base material (matrix).The median size of island phase can be selected sample arbitrarily from amplify 10,000 times photograph with the infiltration type electron microscope, it is measured.Specifically, the length of the whole islands phase in the electron micrograph and width are added up and average, with its median size as the island phase.
In addition, the gel fraction of thermoplastic elastomer of the present invention is below the 30 weight %.
The gel fraction of the thermoplastic elastomer that the present invention is correlated with is preferably below the 20 weight %, below more preferably little 10 weight %.Lower limit is not particularly limited, and also can be the 0 weight % that does not contain crosslinked body.The measuring method of gel fraction is as described below.
[measuring method of gel fraction]
Weighing thermoplastic elastomer particle 100mg is contained in the 325 purpose sieves as sample, it is immersed in the p-Xylol of the 30ml that measures fully concerning particle in encloses container, keeps 140 ℃ of temperature 24 hours.
Then, take out this sample to filter paper, 80 ℃ of dryings more than 2 hours up to constant weight.Gel fraction can be represented by the formula.
Gel fraction [weight %]=[the samples dried weight before the samples dried weight behind the p-Xylol dipping/p-Xylol dipping] * 100
The content of the uncrosslinked vinyl composition of thermoplastic elastomer of the present invention (vinyl resins or vinyl rubber), be preferably 5～40 weight %, more preferably 10～35 weight %, be preferably 15 weight %～30 weight % especially.The content of uncrosslinked vinyl composition (vinyl resins, vinyl rubber) can be obtained from gel fraction.Olefin hydrocarbons thermoplasticity elastic body majority of the present invention is that marine facies are that uncrosslinked composition, island are crosslinked composition mutually.
Here as the vinyl resins composition, can enumerate high density polyethylene(HDPE), new LDPE (film grade), straight-chain low density polyethylene etc.As the vinyl rubber constituent, wherein optimal ethylene-acrylic rubber, ethene-1-butylene interpolymer rubber, ethene-1-hervene copolymer body rubber, ethene-1-octene-1 interpolymer rubber, ethylene-propylene-1-butylene interpolymer rubber etc.Such thermoplastic elastomer fusion bonding on above-mentioned vulcanized rubber formed body the time, is easily produced on mother metal when stretch release and destroys.
The manufacture method of olefin hydrocarbons thermoplasticity elastic body of the present invention then is described.
Olefin hydrocarbons thermoplasticity elastic body of the present invention can be by the mixture that will be made of olefine kind resin and olefines rubber, in the presence of linking agent or do not have under the situation of linking agent, carries out dynamic thermal treatment and obtains.
In addition, also can be in the presence of linking agent or do not have to carry out dynamic thermal treatment under the situation of linking agent and in the thermoplastic elastomer that obtains, further add the olefine kind resin and/or the olefines rubber constituent (preferred above-mentioned vinyl composition) of non-crosslinked and carry out dynamic thermal treatment and obtain olefin hydrocarbons thermoplasticity elastic body of the present invention at the mixture that will constitute by olefine kind resin and olefines rubber.
The cooperation ratio of raw material olefin resinoid, olefines rubber can suitably determine, and will make the content of the olefine kind resin in the thermoplastic olefin elastomer composition that finally obtains surpass 10 weight %.
The degree of crystallinity of measuring with differential scanning calorimeter (DSC) in the thermoplastic elastomer of the present invention is the amount of the olefine kind resin more than 10%, can obtain in order to following method: thermoplastic elastic body and function ebullient dimethylbenzene is extracted, its soluble part precipitates with methyl ethyl ketone, obtains from the weight and the differential scanning calorimeter (DSC) of the polymkeric substance that obtains.
In addition, by the usage quantity of control linking agent, the olefine kind resin of the crosslinked back non-crosslinked that adds and/or the amount of olefines rubber constituent, the content of the gel fraction that can achieve the goal, uncrosslinked vinyl composition.
[olefine kind resin]
The raw material olefin resinoid of thermoplastic elastomer of the present invention, the degree of crystallinity of measuring with differential scanning calorimeter (DSC) is more than 10%.
Melt flow (the MFR of such olefine kind resin; ASTMD1238,190 ℃, load 2.16kg) is preferably 0.01～500g/0 branch, 0.1～100g/10 branch more preferably.
As olefine kind resin of the present invention, can enumerate the homopolymer or the interpolymer of the alpha-olefin of carbonatoms 2～20, preferred carbonatoms 2～10.As above-mentioned alpha-olefin, can enumerate the material identical with above-mentioned alpha-olefin.As above-mentioned olefine kind resin, can enumerate polyethylene, polypropylene etc., preferred especially new LDPE (film grade), straight-chain low density polyethylene, high density polyethylene(HDPE), polypropylene.As new LDPE (film grade), straight-chain low density polyethylene, high density polyethylene(HDPE), polypropylene, can use with the olefine kind resin project of in above-mentioned vulcanized rubber, adding in identical new LDPE (film grade), straight-chain low density polyethylene, high density polyethylene(HDPE), the polypropylene of material that illustrate.
The density of high density polyethylene(HDPE) (ASTM D 1505) surpasses 0.94g/cm 3, preferred 0.945～0.980g/cm 3, more preferably 0.950～0.975g/cm 3
This high density polyethylene(HDPE) is ethylene homo body or the crystallinity ethylene alpha-olefin interpolymers that is made of the alpha-olefin of ethene and carbonatoms 3～20, preferred carbonatoms 3～8.When containing comonomer, the content of its comonomer is few, and 25 moles that are integral body below the %.
Specifically, can enumerate ethene-1-butylene interpolymer, ethylene-propylene copolymer body, ethylene-octene interpolymer etc.
[olefines rubber]
The raw material olefin class rubber of thermoplastic elastomer of the present invention is discontented with 10% with the degree of crystallinity that differential scanning calorimeter (DSC) is measured.The alpha-olefin content that olefines rubber of the present invention is carbonatoms 2～20 is the above amorphous random elastomeric interpolymers of 50 moles of %, the alpha-olefin-nonconjugated diene interpolymer that can enumerate the amorphism alpha-olefin interpolymer that is made of alpha-olefin more than 2 kinds, is made of alpha-olefin and non-conjugated diene more than 2 kinds etc.
As the concrete example of such olefines interpolymer rubber, can enumerate following rubber.
(1) ethene-alpha-olefin interpolymer rubber [ethylene/alpha-olefin (mol ratio)=90～50/10～50 (with ethene and alpha-olefin add up to 100)]
(2) ethylene ' alpha '-olefin-non-conjugated diene interpolymer rubber [ethylene/alpha-olefin/nonconjugated diene (mol ratio)=90～50/10～50/0.1～10 (with ethene, alpha-olefin, non-conjugated diene add up to 100)]
Specifically can enumerate above-mentioned alpha-olefin as above-mentioned alpha-olefin.
In addition,, specifically can enumerate above-mentioned non-conjugated diene, preferred dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methene norbornene, ethylidene norbornene etc. as above-mentioned non-conjugated diene.
The mooney viscosity of these interpolymer rubber [ML1+4 (100 ℃)] preferred 10～250, preferred especially 40～150.In addition, the iodine number of above-mentioned (2) ethylene-alpha-olefin-nonconjugated diene interpolymer rubber is preferably below 25.
In the above-mentioned olefines interpolymer rubber, especially preferably use ethylene-propylene-non-conjugated diene interpolymer rubber.
The rubber of using among the present invention is except above-mentioned olefines interpolymer rubber, can also enumerate olefines interpolymer rubber rubber in addition, for example styrene butadiene ribber (SBR), nitrile rubber (NBR), natural rubber (NR), isoprene-isobutylene rubber elastoprenes such as (IIR), SEBS, polyisobutene etc.
[linking agent]
As the linking agent of using among the present invention, can enumerate for example phenol vulcanizing agents such as organo-peroxide, sulphur, sulfide, phenolic resin etc., wherein preferably use organo-peroxide.
Specifically can enumerate as organo-peroxide, dicumyl peroxide, ditertiary butyl peroxide, 2,5-dimethyl-2,5-two (t-butylperoxy) hexane, 2,5-dimethyl-2,5-two (t-butylperoxy) hexane-3,1, two (t-butylperoxy sec.-propyl) benzene of 3-, 1,1-bis(t-butylperoxy)-3,3, the 5-trimethyl-cyclohexane, normal-butyl-4,4-bis(t-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl superoxide, 2,4 dichlorobenzoyl peroxide, t-butyl peroxy benzoic ether (tert-butyl peroxy benzoate), t-butylperoxyl benzoate (tert-Butyl perbenzoate), tert-butyl peroxide sec.-propyl carbonic ether, diacetyl peroxide, lauroyl peroxide (lauroyl peroxide), t-tutyl cumyl peroxide etc.
Wherein, from smell, coking stability, preferred 2,5-2,2,5-dimethyl-2,5-two (t-butylperoxy) hexane-3,1, two (t-butylperoxy sec.-propyl) benzene, 1 of 3-, 1-bis(t-butylperoxy)-3,3,5-trimethyl-cyclohexane and normal-butyl-4,4-bis(t-butylperoxy) valerate, wherein most preferably 1, two (t-butylperoxy sec.-propyl) benzene of 3-.
With respect to the total amount of 100 weight part olefine kind resins and olefines rubber, this organo-peroxide usage ratio is 0.01～0.4 weight part, preferably uses about 0.03～0.3 weight part.
Among the present invention, when carrying out crosslinking Treatment with above-mentioned organo-peroxide, can mix sulphur, the p-quininie dioxime, p, p '-dibenzoyl quininie dioxime, N-methyl-N, the 4-dinitrosoaniline, oil of mirbane, vulkacit D, TriMethylolPropane(TMP)-N, N '-crosslinking coagents such as m-phenylene dimaleimide, perhaps Vinylstyrene, triallyl cyanurate (triallyl cyanurate), ethylene glycol dimethacrylate, the Diethylene Glycol dimethacrylate, polyethylene glycol dimethacrylate, Viscoat 295, multi-functional methacrylate monomer such as allyl methyl acrylate, multi-functional vinyl monomers such as vinyl butyrate or vinyl stearate ester.By such compound, can obtain evenly and the demulcent crosslinking reaction.Particularly, among the present invention, if use Vinylstyrene, operation easily, good with the intermiscibility of above-mentioned object being treated olefine kind resin or olefines rubber, and, the effect of organo-peroxide solubilize had, dispersing auxiliary as organo-peroxide works, therefore, even by the cross-linking effect that thermal treatment is carried out, can access mobile and rerum natura equilibrated composition.
In the present invention, the such crosslinking coagent or the combined amount of multi-functional vinyl monomer are measured 100 weight % with respect to the total of olefine kind resin and olefines rubber, are generally the scope of 0.01～0.4 weight %, preferred especially 0.03～0.3 weight %.
[other composition]
In the scope of not damaging purpose of the present invention, in olefin hydrocarbons thermoplasticity elastic body of the present invention, can also mix additives such as tenderizer, surface slip agent (slip agent), weighting agent, antioxidant, weather stablizer, tinting material as required.
Dynamic thermal treatment then is described.So-called " carrying out dynamic thermal treatment " is meant and carries out mixing (below, identical) under molten state.
Dynamic thermal treatment among the present invention is preferably carried out in the device of non-style of opening, in addition, preferably carries out under atmosphere of inert gases such as nitrogen, carbon dioxide.
This melting temperature is generally 150～280 ℃, is preferably 170～240 ℃.Mixing time normally 1～20 minute is preferably 3～10 fens.In addition, the shearing force that applies is to count 10～100 with velocity of shear, 000sec -1, be preferably 100～50,000sec -1
Kneading device can use mixing roll (mixing roll), intensive mixer (for example Banbury, kneading machine), single shaft or biaxial extruder etc., but the device of preferred non-style of opening.
Melt flow (the MFR of that obtain as described above, olefin hydrocarbons thermoplasticity elastic body of the present invention; ASTMD1238,230 ℃, load 2.16kg) be generally 0.01～1000g/10 branch, be preferably 0.05～500g/10 branch, 0.1～100g/10 branch more preferably.Melt flow is the thermoplastic elastomer in the above-mentioned scope, and formability is good.
Molded composite material
Molded composite material of the present invention obtains by bonding preferred welding olefin hydrocarbons thermoplasticity elastic body on above-mentioned vulcanized rubber formed body.
The tackiness of the bound fraction of molded composite material of the present invention, the stripping strength that records in stripping test described later are more than the 40MPa, are preferably more than the 45MPa, almost can't see interface peel, and the destructive rate of base material is more than 80%, is preferably more than 90%.
The composite shaped body of vulcanized rubber forming composition of the present invention and thermoplastic elastomer is preferred for the inside/outside decorative material of automobile, is specially adapted to automobile with weather strip (weather strip).In addition, vulcanized rubber formed body of the present invention is not only limited to weather strip, can also be used for need with other purposes of the cementability of thermoplastic elastomer.
In addition, the weather strip material means the sealing material of automobile in the present invention, can enumerate gasket (door weather strip), hood weather strip (bonnet weather strip), glass-run channel (glass run channel) etc.
Specifically, vulcanized rubber extrusion moulding thing is cut out, connect from different direction obtain cut out the corner part that is shaped between the extrudate time, the temperature of olefin hydrocarbons thermoplasticity elastic body more than fusing point carried out jet moulding, obtain by contacting welding with the vulcanized rubber extrusion molding article.
For by vulcanized rubber formed body of the present invention and olefin hydrocarbons thermoplasticity elastic body formed body weather strip that constitute, that have corner part, be described in detail based on Fig. 1.
Fig. 1 be the explanation automobile weather strip (glass-run channel) with and the schematic isometric of forming method.
Shown in Fig. 1 (A), weather strip is cut out extrusion moulding thing 1,2 and this is cut out the joint corner piece 3 that forms when extrusion moulding thing 1,2 is connected from different directions and constitute by vulcanized rubber system.This cuts out extrusion moulding thing the 1, the 2nd,, be after the passage shape with the vulcanized rubber extrusion moulding, be cut into the material of specified length.This length direction of cutting out extrusion moulding thing 1,2 is a rectilinear form.In addition, so-called here " joint corner piece " is, the parts of the thermoplastic elastic system that forms when the extrusion moulding thing of cutting out is connected from different directions.
Such weather strip can be made in accordance with the following methods.
At first, use in injection molding metal pattern 4 is heated in advance the temperature of regulation.Then, shown in Fig. 1 (B), in this metal pattern 4, insert by what vulcanized rubber constituted and cut out extrusion moulding thing 1,2.
Then, though it is not shown, but olefin hydrocarbons thermoplasticity elastic body that will (in the spirochete) temperature more than fusing point is melted in heating chamber, be injected into the die cavity of metal pattern 4 and the position, space between the core rod, in welding on the cross section of cutting out extrusion moulding thing 1,2 after the above temperature fused of fusing point olefin hydrocarbons thermoplasticity elastic body, cool off this thermoplastic elastomer, obtain the weather strip shown in Figure 1A with corner piece 3.
[embodiment]
With embodiment the present invention is described below, but the present invention is not limited to these embodiment.
In addition, hardness, tensile strength, the elongation of the vulcanized rubber formed body that embodiment and comparative example are used, polyethylene of using in embodiment and the comparative example and polyacrylic fusing point (Tm), the mensuration of peeling off form and evaluation when the melt flow of the olefin hydrocarbons thermoplasticity elastic body of using in embodiment and the comparative example (MFR), hardness, tensile strength, elongation, stretch release are carried out according to the methods below.
(1) hardness
With JIS K6301 is benchmark, has measured Xiao A hardness.
(condition determination) makes thin slice with impact molding machine, with A type tester, directly reads scale after the probe contact.
(2) tensile strength and elongation
With JIS K6301 is benchmark, carries out tension test according to following condition, tensile strength and elongation when having measured fracture.
(test condition) makes thin slice with impact molding machine, uses the JIS3 test film to carry out under the condition that punching stretch speed 200mm/ divides.
(3) melt flow (MFR)
The melt flow of olefin hydrocarbons thermoplasticity elastic body is to be benchmark with ASTM D 1238-65T, at 230 ℃, measures under the condition of load 2.16kg.
(4) stretch release intensity and the destruction form when peeling off, aftermentioned.
(reference example 1)
(modulation of vulcanized rubber thin slice)
Will be with respect to the oil-filled ethylene-propylene of 100 weight parts-5-ethylidene-2-norbornene copolymer rubber (ethylene content: 68 moles of %, propylene content: 32 moles of %, iodine number: 12, mooney viscosity [ML 1+4(125 ℃)] 63, oil-filled amount: with respect to 100 parts by weight of rubber, fill paraffin class process oil (bright dipping and product (strain) production, trade(brand)name PW-380) 10 weight parts), the rubber combination (hereinafter to be referred as EPT-1) that contains 20 weight part block PP (230 ℃, the MFR=35g/10 branch, Tm=161 of load 2.16kg ℃, ethene amount 5.6wt%) uses as crude rubber.With the Banbury [manufacturing of (strain) Kobe Steel, BB-2 shape mixing roll] of 1.7 liters of volumes, that the calcium oxide [aboveground lime industry (strain), trade(brand)name: VESTA-BS] of No. 3, the zinc white of the stearic acid of the lime carbonate [shiraishi calcium (strain), trade(brand)name: Whiton SB] of the crude rubber EPT-1 of 130 weight parts, the FEF level carbon black of 165 weight parts [rising sun carbon (strain) produces, trade(brand)name: rising sun #60G], 30 weight parts, the tenderizer of 82 weight parts [bright dipping and product (strain) production, trade(brand)name PW-380)], 1 weight part, 5 weight parts, 5 weight parts is mixing.
Compounding process is, at first with pre-mixing 1 minute of crude rubber, then add carbon black, lime carbonate, tenderizer, stearic acid, No. 3, zinc white, promoting agent carry out 2 minutes mixing.Afterwards, piston is risen clear away, further obtained rubber stock (I) 1670g in mixing 2 minutes.This is mixing to be to carry out for 75% time at filling ratio, and it is mixing further to carry out 3 intermittences according to identical order, obtains 5010g altogether.
Weighing 3670g from the rubber stock (I) that obtains, it is coiled in 14 inches rollers (Japanese ROLL (strain) manufacturing) (60 ℃ of preceding roll surface temperatures, 60 ℃ of back roll surface temperatures, preliminary roller rotating speed 16rpm, back roller rotating speed 18rpm) on, add 1.5 weight part sulphur in this rubber compound (I), 0.5 weight part 2-mercaptobenzothiazole [three new chemical industry (strain) system, trade(brand)name: Sunseller M], 1.0 weight part tetramethyl-thiuram disulfide [three new chemical industry (strain) system, trade(brand)name: Sunseller TT], (Japanese ROLL (strain) makes with 14 inches open forming rolls, 60 ℃ of roller temperature) mixing 7 minutes, obtain rubber stock (II).
With the 150ton press rubber stock (II) heating under 170 ℃ is carried out sulfidization molding in 10 minutes, make the flat board of long 12cm, wide 14.7cm, thick 2mm.Obtained vulcanized rubber flat board (following abbreviation vulcanized rubber formed body-1) like this.
(reference example 2)
With Han Shi mixing machine (Henshel mixer) thorough mixing 15 weight part high density polyethylene(HDPE)s [density (ASTM D 1505): 0.956g/cm 3, MFR (1238,190 ℃ of ASTM D, load 2.16kg): 6g/10 branch, fusing point (Tm): 127 ℃; Hereinafter to be referred as HDPE-1],
The oil-filled ethylene-propylene of 55 weight parts-5-ethylidene-2-norbornene copolymer rubber [ethylene content: 78 moles of %, propylene content: 22 moles of %, iodine number: 13, mooney viscosity [ML 1+4(100 ℃)] 74, oil-filled amount: with respect to 100 parts by weight of rubber, fill paraffin class process oil (bright dipping and product (strain) produce, trade(brand)name PW-380) 40 weight parts; Hereinafter to be referred as EPT-2) as rubber constituent,
30 weight parts propylene-ethylene-1-butylene terpolymers [MFR (1238,230 ℃ of ASTM D, load 2.16kg): 7.0g/10 branch, fusing point (Tm): 136 ℃; Hereinafter to be referred as PP-1] as polypropylene,
0.1 weight part phenol antioxidant [Japanese Ciba-Geigy (strain) make, trade(brand)name: IRGANOX 1010] as antioxidant,
0.1 weight part diazonium class weather stablizer [Japanese Ciba-Geigy (strain) make, trade(brand)name: Tinubine 326] as the weather stablizer,
0.08 weight part organo-peroxide [Japanese grease (strain) make, trade(brand)name Perhexa 25B] as linking agent,
0.06 weight part Vinylstyrene (DVB) as crosslinking coagent,
From forcing machine [article number: TEM-50, toshiba machine (strain) system, 120 ℃ of L/D=40, cylinder temperature: C1～C2,180 ℃ of 140 ℃ of C3～C4, C5～C6,220 ℃ of 200 ℃ of C7～C8, C9～C12, dice temperature: 210 ℃, revolution speed of screw: 200rpm, extrusion capacity: 40kg/h] Yi Bian inject 20 weight part paraffin class process oils [bright dipping and product (strain) produce, trade(brand)name PW-380], carry out granulation on one side, obtain the particle (thermoplastic elastomer-1) of thermoplastic elastomer.
(reference example 3)
With the oil-filled ethylene-propylene of Han Shi mixing machine thorough mixing 70 weight parts-5-ethylidene-2-norbornene copolymer rubber (EPT-2) as rubber constituent,
30 weight parts propylene-ethylene-1-butylene terpolymers [MFR (1238,230 ℃ of ASTM D, load 2.16kg): 7.0g/10 branch, fusing point (Tm): 136 ℃; Hereinafter to be referred as PP-1] as polypropylene,
0.1 weight part phenol antioxidant [Japanese Ciba-Geigy (strain) make, trade(brand)name: IRGANOX 1010] as antioxidant,
0.1 weight part diazonium class weather stablizer [Japanese Ciba-Geigy (strain) make, trade(brand)name: Tinubine 326] as the weather agent,
0.32 weight part organo-peroxide [Japanese grease (strain) make, trade(brand)name Perhexa25B] as linking agent,
0.24 weight part Vinylstyrene (DVB) is as crosslinking coagent,
From forcing machine [article number: TEM-50, toshiba machine (strain) system, 120 ℃ of L/D=40, cylinder temperature: C1～C2,180 ℃ of 140 ℃ of C3～C4, C5～C6,220 ℃ of 200 ℃ of C7～C8, C9～C12, die temperature: 210 ℃, revolution speed of screw: 200rpm, extrusion capacity: 40kg/h] Yi Bian inject 20 weight part paraffin class process oils [bright dipping and product (strain) produce, trade(brand)name PW-380], carry out granulation on one side, obtain the particle (thermoplastic elastomer-2) of thermoplastic elastomer.
(embodiment 1)
The rerum natura of vulcanized rubber formed body-1 and thermoplastic elastomer-1 is as shown in table 1.
Implement moulding with 100ton jet molding machine, make this thermoplastic elastomer-1 melting adhered on the cross section of above-mentioned vulcanized rubber formed body-1, moulding in its jet molding stage.The moulding product that obtain are carried out following stretch release test.
The stretch release test of＜moulding product 〉
The formed body that forms for the formed body that constitutes by vulcanized rubber formed body and thermoplastic elastomer bonding, promptly, the weather strip of Fig. 1, tightly clamp the two ends of adhesive joint portion, carry out tension test with draw speed 200mm/ branch, cross section after the viewing test is confirmed to be the destruction or the interface peel of base material, with peel off thermoplastic elastomer residual on the cross section with respect to the ratio of bonding plane as the wood destruction rate.Its result is as shown in table 1.
(embodiment 2)
In reference example 1, replace EPT-1, obtain vulcanized rubber formed body-2 with following EPT-3.Except using vulcanized rubber formed body-2 to replace testing in the same manner with embodiment the vulcanized rubber formed body-1 of embodiment 1.Evaluation result is as shown in table 1.
EPT-3
Except with respect to the oil-filled ethylene-propylene of 100 weight parts-5-ethylidene-2-norbornene copolymer rubber (ethylene content: 68 moles of %, propylene content: 32 moles of %, iodine number: 12, oil-filled amount:, fill paraffin class process oil (bright dipping and product (strain) are produced, trade(brand)name PW-380) 10 weight parts, mooney viscosity [ML with respect to 100 parts by weight of rubber 1+4(100 ℃)] 63), use and to contain 12 weight part new LDPE (film grade)s (190 ℃, MFR=1.6g/10 branch, the density 0.920g/cm of 2.16kg load 3), 8 weight part straight-chain low density polyethylenes (190 ℃, MFR=1.6g/10 branch, the density 0.921g/cm of 2.16kg load 3) rubber combination (hereinafter to be referred as EPT-3) outside, carry out in the same manner with reference example 1, obtain vulcanized rubber formed body-2.
(comparative example 1)
Use ethylene-propylene-5-ethylidene-2-norbornene copolymer rubber [ethylene content: 68 moles of %, propylene content: 32 moles of %, iodine number: 12, oil-filled amount:, fill paraffin class process oil (bright dipping and product (strain) production, trade(brand)name PW-380) 10 weight parts, mooney viscosity [ML with respect to 100 parts by weight of rubber 1+4(100 ℃)] 63) replace the EPT-1 of reference example 1, use FEF level carbon black [rising sun CARBON (strain) makes, trade(brand)name: rising sun #60G] 185 weight parts, obtain vulcanized rubber formed body-3.Except using vulcanized rubber formed body-3 to replace carrying out in the same manner with embodiment 1 the vulcanized rubber formed body-1 of embodiment 1.Evaluation result is as shown in table 1.
(comparative example 2)
Except the thermoplastic elastomer-2 that uses reference example 3 replaces carrying out in the same manner with embodiment 1 thermoplastic elastomer-1 of embodiment 1.Evaluation result is as shown in table 1.
(comparative example 3)
Except using vulcanized rubber formed body-2 to replace carrying out in the same manner with comparative example 2 the vulcanized rubber formed body-1 of comparative example 2.Evaluation result is as shown in table 1.
(comparative example 4)
Except using thermoplastic elastomer-2 to replace carrying out in the same manner with comparative example 1 thermoplastic elastomer-1 of comparative example 1.Evaluation result is as shown in table 1.
(embodiment 3)
Mix the particle of 85 weight part thermoplastic elastomers-2 and 15 weight part straight-chain low density polyethylenes (190 ℃, MFR=8g/10 branch, the density 0.920g/cm of 2.16kg load with the TEM forcing machine 3), obtain thermoplastic elastomer-3.Then, except using thermoplastic elastomer-3 to replace carrying out in the same manner with embodiment 2 thermoplastic elastomer-1 of embodiment 2.
Evaluation result is as shown in table 1.
[comparative example 5]
Except using thermoplastic elastomer-3 to replace carrying out in the same manner with comparative example 1 thermoplastic elastomer-1 of comparative example 1.Evaluation result is as shown in table 1.
Table 1a
Summary Embodiment 1 Embodiment 2 Embodiment 3
The vulcanized rubber formed body Vulcanized rubber formed body-1 Olefin resin content Weight % 4.8PP
Vulcanized rubber formed body-2 Weight % 4.8PE 4.8PE
Vulcanized rubber formed body-3 Weight %
Thermoplastic elastomer Thermoplastic elastomer-1 Gel fraction wt％ 8 8
Add non-crosslinked vinyl composition - Do not have Do not have
Thermoplastic elastomer-2 Gel fraction wt％
Add non-crosslinked vinyl composition -
Thermoplastic elastomer-3 Gel fraction wt％ 28
Add non-crosslinked vinyl composition - Have
Non-crosslinked vinyl composition addition wt％ 15
The rerum natura of vulcanized rubber formed body Hardness Shore A 77 79 79
Tensile strength MPa 12.9 11.4 11.4
Elongation ％ 290 270 270
The rerum natura of thermoplastic elastomer MFR g/10min 1.2 1.2 4.2
Hardness Shore A 84 84 85
Tensile strength MPa 6.7 6.7 8.9
Elongation ％ 700 700 600
The cementability of vulcanized rubber and thermoplastic elastomer Bonding stripping strength MPa 46 45 46
Destruction form when peeling off - Wood destruction Wood destruction Wood destruction
The wood destruction rate ％ 100 80 80
Table 1b
Summary Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5
The vulcanized rubber formed body Vulcanized rubber formed body-1 Olefin resin content Weight % 4.8PP
Vulcanized rubber formed body-2 Weight % 4.8PE
Vulcanized rubber formed body-3 Weight % 0 ?0
Thermoplastic elastomer Thermoplastic elastomer-1 Gel fraction wt％ 8
Add non-crosslinked vinyl composition Do not have
Thermoplastic elastomer-2 Gel fraction wt％ 37 37 37
Add non-crosslinked vinyl composition Do not have Do not have Do not have
Thermoplastic elastomer-3 Gel fraction wt％ 28
Add non-crosslinked vinyl composition - Have
Non-crosslinked vinyl composition addition wt％ 15
The rerum natura of vulcanized rubber formed body Hardness Shore A 77 77 79 77 77
Tensile strength MPa 12.2 12.9 11.4 12.2 12.2
Elongation ％ 200 290 270 200 200
The rerum natura of thermoplastic elastomer MFR g/10min 1.2 3.4 3.4 3.4 4.2
Hardness Shore A 84 83 83 83 85
Tensile strength MPa 6.7 8.1 8.1 8.1 8.9
Elongation ％ 700 610 610 610 600
The cementability of vulcanized rubber and thermoplastic elastomer Bonding stripping strength MPa 41 43 43 40 42
Destruction form when peeling off - Wood destruction Interfacial failure Interfacial failure Interfacial failure Wood destruction
The wood destruction rate ％ 50 0 0 0 40
Utilizability on the industry
When melting adhered olefin hydrocarbons thermoplasticity elastic body can be provided according to the present invention and not use bonding agent, make on the vulcanized rubber formed body, can form have sufficient adhesive strength and produce when peeling off wood destruction formed body the vulcanized rubber formed body with and melting adhered formed body.
This molded composite material is suitable for automobile inside/outside decorative material usefulness, particularly weather strip purposes.

Claims (3)

1. molded composite material is characterized in that:
Engage by vulcanized rubber formed body (1) and the formed body (2) that constitutes by thermoplastic elastomer and to form, wherein,
In the described vulcanized rubber formed body (1), gross weight with the vulcanized rubber formed body is 100 weight %, the crystallization degree with differential scanning type calorimeter mensuration that contains 2～10 weight % is the olefine kind resin more than 10%, and described olefine kind resin is 0.870～0.94g/cm for being selected from polypropylene, polybutene and ASTMD1505 density 3New LDPE (film grade) or straight chain shape new LDPE (film grade) at least a,
In the described thermoplastic elastomer, the gross weight of the formed body that constitutes with thermoplastic elastomer is 100 weight %, contain the crystallization degree that surpasses 10 weight % and be the olefine kind resin more than 10% with differential scanning type calorimeter mensuration, and the gel fraction of described thermoplastic elastomer is below the 30wt%, and has island structure.
2. molded composite material as claimed in claim 1 is characterized in that: molded composite material is used for the automobile inside/outside decorative material.
3. molded composite material as claimed in claim 2 is characterized in that: the automobile inside/outside decorative material is a weather strip.
CNB2004800102921A 2003-04-17 2004-04-05 Composite formed article comprising vulcanized rubber and thermoplastic elastomer and use thereof Expired - Fee Related CN100355818C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2003112630 2003-04-17
JP112630/2003 2003-04-17

Publications (2)

Publication Number Publication Date
CN1774466A CN1774466A (en) 2006-05-17
CN100355818C true CN100355818C (en) 2007-12-19

Family

ID=33296061

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB2004800102921A Expired - Fee Related CN100355818C (en) 2003-04-17 2004-04-05 Composite formed article comprising vulcanized rubber and thermoplastic elastomer and use thereof

Country Status (5)

Country Link
US (1) US20060188739A1 (en)
JP (1) JP4615441B2 (en)
CN (1) CN100355818C (en)
GB (1) GB2417489B (en)
WO (1) WO2004092255A1 (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7326471B2 (en) * 2004-10-15 2008-02-05 Advanced Elastomer Systems, L.P. Corner molding compositions for automotive sealant systems
CN101674934A (en) * 2007-03-23 2010-03-17 住友化学株式会社 Composite molded object and process for producing composite molded object
CN101670771B (en) * 2008-09-10 2012-06-20 南通江洲工程材料科技有限公司 Combined thermoplastic elastic body for automotive glass guide groove sealing strip and production method thereof
US10619037B2 (en) 2017-11-21 2020-04-14 Johns Manville Roofing compositions comprising linear low density polyethylene
US11511610B2 (en) 2018-11-12 2022-11-29 Shape Corp. Vehicle door carrier with integrated edge seal and method of manufacture
US11432536B2 (en) * 2020-09-11 2022-09-06 Central Gargen & Pet Company Aquarium conversion systems

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001270042A (en) * 2000-03-24 2001-10-02 Toyoda Gosei Co Ltd Rubber/thermoplastic elastomer composite material
US20030059637A1 (en) * 2001-08-31 2003-03-27 Mitsui Chemicals, Inc. Olefin thermoplastic elastomer, process for producing the same and use thereof

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3322066B2 (en) * 1995-03-31 2002-09-09 ジェイエスアール株式会社 Thermoplastic elastomer composition with excellent injection fusion property
JP3598487B2 (en) * 1997-03-27 2004-12-08 豊田合成株式会社 Automotive weather strip
US5889119A (en) * 1997-07-17 1999-03-30 The University Of Akron Thermoplastic rubbery compositions
JP3505701B2 (en) * 1997-11-06 2004-03-15 豊田合成株式会社 Foamed rubber extrudate
ES2225519T3 (en) * 2000-04-21 2005-03-16 Jsr Corporation COMPOSITION OF ELASTOMERO THERMOPLASTIC.
JP3881271B2 (en) * 2001-03-29 2007-02-14 三井化学株式会社 Thermoplastic elastomer composition and use thereof
JP3794950B2 (en) * 2001-11-22 2006-07-12 三井化学株式会社 Olefin-based thermoplastic elastomer, composite molded body, and method for producing composite molded body
JP3821748B2 (en) * 2002-04-26 2006-09-13 三井化学株式会社 Olefin-based thermoplastic elastomer molded body

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001270042A (en) * 2000-03-24 2001-10-02 Toyoda Gosei Co Ltd Rubber/thermoplastic elastomer composite material
US20030059637A1 (en) * 2001-08-31 2003-03-27 Mitsui Chemicals, Inc. Olefin thermoplastic elastomer, process for producing the same and use thereof

Also Published As

Publication number Publication date
CN1774466A (en) 2006-05-17
GB2417489A (en) 2006-03-01
US20060188739A1 (en) 2006-08-24
JP4615441B2 (en) 2011-01-19
JPWO2004092255A1 (en) 2006-07-06
WO2004092255A1 (en) 2004-10-28
GB0523284D0 (en) 2005-12-21
GB2417489B (en) 2007-04-04

Similar Documents

Publication Publication Date Title
KR100495177B1 (en) Olefinic thermoplastic elastomer, method of producing thereof, and use thereof
KR100706088B1 (en) Layered product of olefin foam and use
CN101679702B (en) Thermoplastic elastomer composition
KR100695546B1 (en) Lower foggy thermoplastic elastomer composition, and process for producing the composition and its use
CA2377688A1 (en) Thermoplastic elastomer composition
CN101497716B (en) Thermoplastic elastomer composition, composite molded body and weather strip
CN101921433A (en) Compositions of vulcanize rubbers
JPWO2002081958A1 (en) Hose made of thermoplastic elastomer
CN100355818C (en) Composite formed article comprising vulcanized rubber and thermoplastic elastomer and use thereof
JP2020117649A (en) Thermoplastic resin composition, molding using the same, and use of the same
JP3952392B2 (en) Olefin-based thermoplastic elastomer, method for producing the same, and use thereof
CN101668810B (en) Method of producing thermoplastic elastomer composition and molded article
JP3794950B2 (en) Olefin-based thermoplastic elastomer, composite molded body, and method for producing composite molded body
JP5139702B2 (en) Thermoplastic elastomer composition and use thereof
JP2010280777A (en) Rubber composition and rubber molded product
JP2009215356A (en) Thermoplastic elastomer composition
JP4927460B2 (en) Olefinic thermoplastic elastomer and its use
JP4875365B2 (en) Thermoplastic elastomer composition
JP3853230B2 (en) Shape memory elastomer composition, shape memory elastomer molding and shape memory elastomer molding
JP5089156B2 (en) Thermoplastic elastomer composition and use thereof
JP3874673B2 (en) Thermoplastic elastomer and its use
JPH10219217A (en) Rubber composition for adhesion
JP4508401B2 (en) Manufacturing method of alloy extrusion molded product, manufacturing apparatus and molded product
JP2020117650A (en) Thermoplastic resin composition, molding using the same, and use of the same

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20071219

Termination date: 20150405

EXPY Termination of patent right or utility model